Process for changing charges of matter



June 14, 1966 J. H. HELLER PROCESS FOR CHANGING CHARGES OF MATTER Filed June 21, 1963 Microns per sec. per cm.

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5 Sheets-Sheet 1 Control Value of Zeta Potential Control Value of Zeta Potential of Untreated Particles of Untreated Particles 0 O. u G) I!) U) C O L- .2 2

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3 a l l l I l l 32 l l I l -l l l Frequency Frequency INVENTOR Jghn H. Heller BY i fmwq 7 M ATTORNEYS June 14, 1966 J. H. HELLER 3,256,168

PROCESS FOR CHANGING CHARGES 0F MATTER Filed June 21, 1963 5 Sheets-Sheet 2 X J: O O O E 3 K :5 Z 5 i I I X O III E d 0 U) 3 O. 8 O E O C Q) X 3 2 n.

suomgm Jed Janmngq 0 INVENTOR E Jpohn H. Heller BY M.m4a W ML MM ATTORNEYS June 14, 1966 J. H. HELLER 3,256,1

. PROCESS FOR CHANGING CHARGES 0F MATTER Filed June 21, 1363 5.Sheets-Sheet 5 8 o o E U o 0 IO L I I I l I m I\ I Q "I N o r v v n v r' w 5 mo lad on JGG'QQS Jad V Amgq'ow (D INVENTOR E John H.HeIler AT ORNEYS June 14, 1966 J. H. HELLER 3,256,168}

PROCESS FOR CHANGING CHARGES 0F MATTER Filed June 21, 1963 5 Sheets-Sheet 4 G.FIG.4.

-O- Elecrrophorefic mobility in distilled warer of 1.1704

diamerer PSL against frequency.

-+- Elecfrophorefic mobility in distilled water of 1.170

diamerer PSL against frequency afrer an initial exposure for optimal mobility reduction at 16 mc/sec. Voltage 500 V/cm; pulse durarion- 10a/sec;'prf500; Time in field lminuie.

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iVlC per second lNVE NTORr John H. Heller ATTORNEYS June 14, 1966 J. H. HELLER PROCESS FOR CHANGING CHARGES OF MATTER 5 Sheets-Sheet 5 Filed June 21, 1963 'um 19d 'oas 13d suozagw Rm ww w m W w a:

This application is a continuation-impart of application Serial No. 853,188, filed November 16, 1959, now Patent No. 3,095,359.

This invention relates to particles of matter having positive or negative charges and has for its object the provision of a process for changing the charges on various forms of matter, including the electrical surface charges.

This invention is based on the discovery that the electrical charges on particles of matter in air or in a liquid suspension under the influence of a particular pulsed radio frequency field can result in a material and significant change in the charge. The change eflected is sensational and unpredictable and not presently explainable on a basis of the input energy which is trivial in comparison with the conventionally accepted energy requirements to effect similar changes.

In accordance with the invention various forms of matter, both organic and inorganic having charges in or on the matter, can be treated by exposure of the matter to the radio frequency field to change the charge characteristics of the matter. Various materials exhibit a specificity with respect to the size of the particles in relation to the radio frequency field, its frequency, voltage and the pulses.

Certain experiments were carried out which confirmed the concept of the invention in modifying the charges on particles of matter. Colloidal suspensions of various materials (described hereinafter) were placed in a cuvette measuring 2 x 2 x 4.5 cm. Two opposing sides were of sheet platinum which served as electrodes, the other two sides and bottom were made of /8 inch sheet polystyrene. The output from a generator was connected to one electrode and the other electrode was connected directly to ground. This also worked if another generator was used and the cuvette was put in a doubleended configuration. It also worked if a tuned coil was placed across the output and if a beaker was put in the center of the coil containing a solution without any contact with the coil whatsoever. In a typical test operation 15 ml. of a suitably diluted suspension of polystyrene latex or other colloid was introduced into the couvette and exposed to the radio frequency field. After exposure the suspension was removed and the electrophoretic mobility was measured.

The electrical equipment used had the capacity to provide a frequency range of 5-50 rnc./sec. with voltage continuously variable from -20,000 volts, peak to peak/ cm. The output was pulsed so that the resulting heat could be controlled. The pulses duration was varied from -100 ,usecs. and the pulse repetition frequency (p.r.f.) was variable from 4-1.000 pulses/sec. The changes in the charges of the particles were determined by electrophoretic mobility evaluations. The electrophoretic mobilities were measured in a cylindrical microelectrophoresis cell of the type described by Bangham et al. 2 (Nat. (London) 182, 642 (1958)). The cell was suspended in a temperature controlled water bath and all measurements were made at 25- *O.5. All electrophoretic results were expressed in microns/sec./ volt/cm. and represent the mean of at least ten determinations.

3,255,168 Patented June 14, 1966 In a series of test operations polystyrene latex (PSL) colloidal suspensions consisting of particles the diameters of which were 1.305;, 1.17 0802 1. and 0.761n were dialyzed to a dilution of 10 times of distilled water and the particle concentrations were determined. In another experiment the PSL particles were coated with gelatin by suspending them in a 5% gelatin solution at 45 C. which was cooled and washed three times by centrifuging in distilled water.

Upon exposure of PSLs of various particle diameters it was found that each size had a specific frequency at which maximum reduction in electrophoretic mobility occured, as shown in FIG. 1. FIG. 2. shows the relationship between the frequency optimum obtained above and the particle diameter. PSL particles having 1.305 diameters wit-h adsorbed gelatin were suspended in diluted Michaelis buffer (of ionic strength 10 M) at pH 3.1 and pH 10.0. In these media the particles were positively and negatively charged respectively. The maximum charge in mobility, in both cases, occurred after exposure at 13.00 mc./sec.; the positive particles became more positively charged and the negative particles became less negative.

The frequency optimum was found not to alter as a function of added salt up to a concentration of 10 M NaCl, although the initial mobilities were diiferent.

The effect of varying the radio frequency voltage upon the decrease in mobility at 16.00 mc./sec. for the 1.170,u diameter particles is shown in FIG. 3. It can be 'seen that there was nofurther reduction above about 500 volts peak to peak/cm. The same held true for the 1.305 p. diameter particles at 13.00 mc./sec. (1). However the plateau for the 0802p and 0.761;; particles at their frequency optima was not reached until ca 1,000 volts peak to peak/cm.

The optimum change in mobility in e.g. the 1.305; diameter particles, when exposed at 13.00 mc./sec. and 500 volts/cm. for one minute, was obtained using a duty cycle of 0.5%, i.e. a 10, sec. pulse at 500 pulses/sec. If the duty cycle was increased, no further change could be induced. However, if the duty cycle was decreased, and the time of exposure increased by the same factor (e.g. increase of time of exposure to 5 mins. and decrease of p.r.f. to then the same results were obtained. If the duty cycle was increased above 0.5%, at a lower voltage however, the reduction of mobility was not as great.

Under the operating conditions described above there was no measurable rise in temperature of the colloidal suspension. If the colloid was cooled to 4 C. or heated to 50 C. before radio frequency exposure, or if heating was induced in the suspension by increasing the radio frequency voltage and/ or duty cycle, the same percentage change in mobility was obtained.

After exposure of a colloid under the condition chosen to produce maximum reduction of mobility, the recovery to the initial mobility as a function of time was measured. The mobility was found to recover linearly with time. Table 1 shows the average time required to recover initial mobilities for the various particle sizes.

TABLE 1,-TIME FOR TO INITIAL MOBILITY It can be seen that the time to recover to the initial mobility approximates to a linear function of particle diameter. However, at 10 salt solution, no recovery was noted.

It was found that the initial mobility of the colloid could be recovered by exposure for a further minute at a frequency other than that required to produce maximum reduction. FIG. 4 shows results obtained by exposing a suspension of 1.170 particles at the frequency and voltage at which maximum reduction in mobility was obtained, i.e. (16.00 me. and 500 volts/cm. for one minute) followed immediately by exposure for an additional minute at another frequency.

Under optimum conditions of frequency and voltage for maximum reduction of mobility, the effect of varying the concentration of polystyrene was explored. FIG. 5 shows that above a certain concentration (i.e. particle/ml), the RF field produced no reduction in mobility of 0.802 diameter PSL and that below a certain concentration (3 10' particles/ml.) there was no further reduction in mobility. However, if a suspension of PSL with a particle concentration of 10 particles/ml. was exposed to the radio frequency field under conditions for maximum reduction of mobility and subsequently diluted, it was found that the mobility of the diluted suspension fell at the same place on the curve as it would have, had it been exposed at this dilution in the first place. See FIG; 5.

The surface of undialyzed PSL consists of an absorbed layer of emulsifier (in this case, an alkyl aryl sulfonate). This layer may be removed by dialysis, but the residual charge is still high and is thought to be due to carboxyl groups (from the oxidation of vinyl side chains) and sulfate groups (from a polymerization chain termination step). These groups are linked to the polymer by covalent --C-C -CS-- bonds. The reduction in electrophoretic mobility is a reflection of a reduction of the surface charge or zeta potential. The same type of change was found in starch particles, in several different size monodisperse of silver iodide, in the micrococci bacteria and on silica particles. The phenomenon then would appear to be general, applying to living, organic and inorganic materials. This change can be achieved in several ways, e.g., by a change in the ionic strength of the medium, but the present important change of in terest is one of surface charge density 6.

The process of the invention is applicable to a wide field of industrial uses. In general, the process has utility in which the changes in the charges on matter can be utilized to effect changes in the chemical or physical use of the matter. Specifically, the changes in the magnitude of the charges on colloidal particles can be changed with- 5 out changing the molecule.

Materials used as detergents, in paints, inks and like materials may be subjected to the radio frequency field to effect changes in the charges. For example, the mineral components of ores in a fine state of subdivision in flotation pulps can be subjeced to the radio frequency 5 field to change the charges to effect a more rapid and complete release of the minerals from the froth. The 'hydratable clays, such as Bentonite clay, are very sensitive to the effect of electrolytes and may be treated to improve the use of the clay for example in well drilling muds.

It is possible, and indeed probable, that the changes on the surface reflect a more profound change on the interior of the particles. In such an event, this is not just a change of charge on the surface, but reflects either a change in crystalline structure or molecular rearrangement, or even molecular modification.

That which is claimed is:

1. The process for reducing the surface negative electrical charges on non-living particles of matter dispersed in a fluid medium which comprises subjecting said dispersed particles to an R-F field having a frequency selected in the range of 5-50 mc./sec. to effect a maximum reduction in the electrophoretic mobility of said particles, the voltage of said field being less than the value required to produce ionization in the fluid dispersed particles.

2. The process for reducing the surface negative electrical charges on non-living particles of matter dispersed in a fluid medium which comprises subjecting said dispersed particles to a pulse modulated R-F field having a frequency selected to effect a maximum reduction in the electrophoretic mobility of said particles, the voltage of said field being less than the value required to produce ionization in the fluid dispersed particles, the pulse modulation frequency varying in range from 41000 pulses/ second and the pulse duration from 5-100 microseconds.

3. In the process of claim 1 subjecting colloidal suspensions in an aqueous medium to said R-F field.

4. In the process of claim 1 subjecting organic chemical compounds in colloidal suspension to said R-F field. 40

References Cited by the Examiner UNITED STATES PATENTS 2,257,177 9/1941 Luster 204168 2,280,771 4/1942 Dufour et al. 204-465 2,553,944 5/1951 Schlesman 204312 X 2,966,469 12/1960 Smythe et al. 204-164 3,095,359 6/1963 Heller -78 0 JOHN H. MACK, Primary Examiner. WINSTON A. DOUGLAS, Examiner. H. S. WILLIAMS, Assistant Examiner. 

1. THE PROCESS FOR REDUCING THE SURFACE NEGATIVE ELECTRICAL CHARGES ON NON-LIVING PARTICLES OF MATTER DISPERSED IN A FLUID MEDIUM WHICH COMPRISES SUBJECTING SAID DISPERSED PARTICLES TO AN R-F FIELD HAVING A FREQUENCY SELECTED IN THE RANGE OF 5-50 MC./SEC. TO EFFECT A MAXIMUM REDUCTION IN THE ELECTROPHORETIC MOBILITY OF SAID PARTICLES, THE VOLTAGE OF SAID FIELD BEING LESS THAN THE VALUE REQUIRED TO PRODUCE IONIZATION IN THE FLUID DISPERSED PARTICLES. 